Thermoplastic polyurethane

ABSTRACT

The present invention relates to thermoplastic polyurethanes obtainable or obtained by reaction of at least one polyisocyanate composition, at least one chain extender (KV1) of general formula (I) and one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of &lt;500 g/mol, and at least one polyol composition. The present invention further relates to a production process for such thermoplastic polyurethanes and to the use of a thermoplastic polyurethane according to the invention or of a thermoplastic polyurethane obtainable or obtained by a process according to the invention for producing extrusion products, films and molded articles.

The present invention relates to thermoplastic polyurethanes obtainableor obtained by reaction of at least one polyisocyanate composition, atleast one chain extender (KV1) of general formula (I) and one furtherchain extender (KV2) selected from the group consisting of compoundshaving at least two isocyanate-reactive groups having a molecular weightof <500 g/mol, and at least one polyol composition. The presentinvention further relates to a production process for such thermoplasticpolyurethanes and to the use of a thermoplastic polyurethane accordingto the invention or of a thermoplastic polyurethane obtainable orobtained by a process according to the invention for producing extrusionproducts, films and molded articles.

Thermoplastic polyurethanes for various applications are known inprinciple from the prior art. By the variation in the feedstocks, it ispossible to obtain different profiles of properties.

WO 2006/082183 A1 for example discloses a process for continuousproduction of thermoplastically processable polyurethane elastomerswherein a polyisocyanate, a compound having Zerewittinoff-activehydrogen atoms having an average molecular weight of 450 g/mol to 5000g/mol, a chain extender and further auxiliary and additive substancesare reacted. Specific profiles of properties are achieved by means ofspecific processing.

EP 0 922 552 A1 also discloses a process for continuous production ofgranulate from thermoplastic polyurethane elastomers, wherein agranulate is initially produced by reaction of organic diisocyanates,difunctional polyhydroxyl compounds having molecular weights of 500 to8000 and difunctional chain extenders having molecular weights of 60 to400 in the presence of catalysts and optionally auxiliaries and/oradditives. Use for producing extruded, injection molded or calendaredproducts, in particular cable sheathings, hoses and/or films, islikewise disclosed.

WO 98/56845 A1 discloses a thermoplastic polymer obtained by reaction ofa polyisocyanate, a glycol as a chain extender and a polyether polyol.Various isocyanates, chain extenders and polyols are disclosed.

Depending on the application the properties of the thermoplasticpolyurethane may be varied via the type of inputs and the employedquantity ratios. For example stability may be influenced by variation ofthe polyol component. Stability may also be influenced by processing,for example by heat treatment. Variation of the hard phases likewisemakes it possible to influence mechanical properties and extrusionquality.

It is often the case, however, that the mechanical properties of athermoplastic polyurethane are inadequate for individual applications.

Proceeding from the prior art it is thus an object of the presentinvention to provide improved materials exhibiting good mechanicalproperties.

According to the invention this object is achieved by a thermoplasticpolyurethane obtainable or obtained by reaction of at least thecomponents (i) to (iii):

-   -   (i) at least one polyisocyanate composition;    -   (ii) at least one chain extender (KV1) of general formula (I),

-   -   -   wherein A is selected from O, N(R3), S, CH₂,            -   Q is selected from O, N(R3), S, CH₂,            -   R1 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                OH,            -   R2 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                CH₂—CH(CH₃)—OH, OH,            -   n is 0, 1, 2, 3, 4, 5 or 6,            -   R3 is selected from CH₃, CH₂—CH₃,            -   and A and Q are not simultaneously CH₂,

    -   (iii) at least one polyol composition,        wherein at least one further chain extender (KV2) selected from        the group consisting of compounds having at least two        isocyanate-reactive groups having a molecular weight of <500        g/mol is employed.

It has been found that, surprisingly, the inventive combination of thecomponents (i) to (iii) made it possible to obtain thermoplasticpolyurethanes exhibiting not only good mechanical properties but alsoimproved extrusion quality. The inventive thermoplastic polyurethanes inparticular exhibit an improved compression set. The optical propertiesof the obtained extrusion products are also markedly improved, forexample through a smoother surface.

According to the invention at least the components (i) to (iii) arereacted. Employed according to the invention as the chain extender is atleast one chain extender (KV1) of general formula (I),

wherein A is selected from O, N(R3), S, CH₂ and Q is selected from O,N(R3), S, CH₂. The radicals R1 and R2 are alkyl radicals which mayoptionally be OH functionalized. R1 is selected from CH₂—(CH₂)_(n)—OH,CH(CH₃)—CH₂—OH, OH, and R2 is selected from CH₂—(CH₂)_(n)—OH,CH(CH₃)—CH₂—OH, CH₂—CH(CH₃)—OH, OH, wherein n is 0, 1, 2, 3, 4, 5 or 6,and R3 is selected from CH₃, CH₂—CH₃. According to the invention A and Qare not simultaneously CH₂. According to the invention, at least onefurther chain extender (KV2) selected from the group consisting ofcompounds having at least two isocyanate-reactive groups having amolecular weight of <500 g/mol is employed.

Suitable compounds employable as chain extenders (KV1) of formula (I)are known per se to those skilled in the art. For example one suitablechain extender (KV1) is hydroquinone bis(2-hydroxyethyl)ether.

In a further embodiment the present invention thus also relates to athermoplastic polyurethane as described hereinabove, wherein the chainextender (KV1) of general formula (I) is hydroquinonebis(2-hydroxyethyl)ether.

Based on the total amount of chain extender the further chain extender(KV2) is typically employed in an amount of 1% to 50%, preferably in anamount of 1% to 30%, more preferably in an amount of 1% to 25%, morepreferably 5% to 20%, particularly preferably in an amount of 5% to 10%.

Compounds having at least two isocyanate-reactive groups are employed asfurther chain extender (KV2). Isocyanate-reactive groups may be, inparticular, NH, OH or else SH groups. Suitable compounds are known perse to those skilled in the art. Diamines or else diols are suitable, forexample. In a further embodiment the present invention accordingly alsorelates to a thermoplastic polyurethane as described hereinabove,wherein the at least one further chain extender is selected fromaliphatic and aromatic diols having a molecular weight of <500 g/mol.

In one embodiment of the present invention diols having a molecularweight of <350 g/mol are employed as further chain extender (KV2). In afurther embodiment the present invention also relates to a thermoplasticpolyurethane as described hereinabove, wherein the at least one furtherchain extender (KV2) is selected from aliphatic and aromatic diolshaving a molecular weight of <350 g/mol.

Further preferably employable are aliphatic, araliphatic, aromaticand/or cycloaliphatic diols having a molecular weight of 50 g/mol to 220g/mol. Preference is given to alkanediols having 2 to 10 carbon atoms inthe alkylene radical, especially di-, tri-, tetra-, penta-, hexa-,hepta-, octa-, nona- and/or decaalkylene glycols. Particularly preferredfor the present invention are 1,2-ethylene glycol, 1,4-butanediol,1,6-hexanediol.

Also suitable as chain extenders (KV2) in the context of the presentinvention are branched compounds such as 1,4-cyclohexyldimethanol,2-butyl-2-ethylpropanediol, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, pinacol, 2-ethyl-1,3-hexanediol,1,4-cyclohexanediol or N-phenyldiethanolamine. Likewise suitable arecompounds having OH and NH groups such as for example 4-aminobutanol.

It is also possible according to the invention to employ further chainextenders. Third and/or fourth chain extenders of this type aretypically employed in amounts of less than 10% based on the amount ofthe employed chain extenders.

In a further embodiment it is possible in the context of the presentinvention to employ as further chain extender (KV2) a compound ofgeneral formula (II):

wherein A is selected from O, N(R3), S, CH₂,

Q is selected from O, N(R3), S, CH₂,

R1 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH, OH,

R2 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH, CH₂—CH(CH₃)—OH,OH,

n is 0, 1, 2, 3, 4, 5 or 6,

R3 is selected from CH3, CH2—CH₃.

It is preferable when the compound of general formula (II) is resorcinolbis(2-hydroxyethyl)ether.

In a further embodiment the present invention accordingly relates to athermoplastic polyurethane as described hereinabove, wherein the atleast one further chain extender (KV2) is a compound of general formula(II):

wherein A is selected from O, N(R3), S, CH₂,

-   -   Q is selected from O, N(R3), S, CH₂,    -   R1 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH, OH,    -   R2 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,        CH₂—CH(CH₃)—OH, OH,    -   n is 0, 1, 2, 3, 4, 5 or 6,    -   R3 is selected from CH₃, CH₂—CH₃.

In a preferred embodiment of the present invention hydroquinonebis(2-hydroxyethyl)ether is employed as chain extender (KV1) of formula(I) and resorcinol bis(2-hydroxyethyl)ether is employed as further chainextender (KV2).

In the context of the present invention the employed amount of the chainextender and the polyol composition may be varied within wide ranges.For example, the component (iii) and the component (ii) are employed ina molar ratio of (iii) to (ii) of 1 to 0.7, 1 to 2.7 and 1 to 7.3.

According to the invention the polyol composition comprises at least onepolyol. Polyols are known in principle to those skilled in the art anddescribed for example in “Kunststoffhandbuch”, volume 7, “Polyurethane”,Carl Hanser Verlag, 3rd edition 1993, chapter 3.1. Particularlypreferably employed as polyols are polyesterols or polyetherols.Polycarbonates may likewise be employed. Copolymers too may be used inthe context of the present invention. The number-average molecularweight of the polyols used according to the invention is by preferencebetween 0.5×10³ g/mol and 8×10³ g/mol, preferably between 0.6×10³ g/moland 5×10³ g/mol, in particular between 0.8×10³ g/mol and 3×10³ g/mol.

Polyetherols but also polyesterols, block copolymers and hybrid polyolssuch as for example poly(ester/amide) are suitable according to theinvention. According to the invention preferred polyetherols arepolyethylene glycols, polypropylene glycols, polyadipates,polycarbonates, polycarbonate diols and polycaprolactone.

In another embodiment the present invention also relates to athermoplastic polyurethane as described hereinabove, wherein the polyolcomposition comprises a polyol selected from the group consisting ofpolyetherols, polyesterols, polycaprolactones and polycarbonates.

Suitable polyols are for example polyetherols such as polytrimethyleneoxide or polytetramethylene oxide.

Suitable block copolymers are for example those having ether and esterblocks, for example polycaprolactone having polyethylene oxide orpolypropylene oxide end blocks, and also polyethers havingpolycaprolactone end blocks. According to the invention preferredpolyetherols are polyethylene glycols and polypropylene glycols.Polycaprolactone is also preferred.

In a particularly preferred embodiment the employed polyol has anumber-average molecular weight Mn in the range from 500 g/mol to 4000g/mol, preferably in the range from 800 g/mol to 3000 g/mol.

In a further embodiment the present invention thus relates to athermoplastic polyurethane as described hereinabove, wherein at leastone polyol present in the polyol composition has a number-averagemolecular weight Mn in the range from 500 g/mol to 4000 g/mol.

Mixtures of different polyols may also be employed according to theinvention. It is preferable when the employed polyols/the polyolcomposition have an average functionality between 1.8 and 2.3,preferably between 1.9 and 2.2, in particular 2. It is preferable whenthe polyols used according to the invention have only primary hydroxylgroups.

In one embodiment of the present invention production of thethermoplastic polyurethane employs as component (iii) at least onepolyol composition comprising at least polytetrahydrofuran. According tothe invention the polyol composition may comprise not onlypolytetrahydrofuran but also further polyols.

Further polyols suitable according to the invention are for examplepolyethers but also polyesters, block copolymers and also hybrid polyolssuch as for example poly(ester/amide). Suitable block copolymers are forexample those having ether and ester blocks, for examplepolycaprolactone having polyethylene oxide or polypropylene oxide endblocks, and also polyethers having polycaprolactone end blocks.According to the invention preferred polyetherols are polyethyleneglycols and polypropylene glycols. Polycaprolactone is also preferred asa further polyol.

In a further embodiment the present invention accordingly relates to athermoplastic polyurethane as described hereinabove, wherein the polyolcomposition comprises at least one polytetrahydrofuran and at least onefurther polyol selected from the group consisting of a furtherpolytetramethylene oxide (PTHF), polyethylene glycol, polypropyleneglycol and polycaprolactone.

In a particularly preferred embodiment the polytetrahydrofuran has anumber-average molecular weight Mn in the range from 500 g/mol to 5000g/mol, more preferably in the range from 550 g/mol to 2500 g/mol,particularly preferably in the range from 650 g/mol to 2000 g/mol.

In the context of the present invention the composition of the polyolcomposition may be varied within wide ranges. For example the content ofthe first polyol, preferably of polytetrahydrofuran, may be in the rangefrom 15% to 85%, preferably in the range from 20% to 80%, morepreferably in the range from 25% to 75%.

According to the invention the polyol composition may also comprise asolvent. Suitable solvents are known per se to those skilled in the art.

Provided that polytetrahydrofuran is employed the number-averagemolecular weight Mn of the polytetrahydrofuran is preferably in therange from 500 to 5000 g/mol. It is more preferable when thenumber-average molecular weight Mn of the polytetrahydrofuran is in therange from 500 to 1400 g/mol.

In a further embodiment the present invention also relates to athermoplastic polyurethane as described hereinabove, wherein the polyolcomposition comprises a polyol selected from the group consisting ofpolytetrahydrofurans having a number-average molecular weight Mn in therange from 500 g/mol to 5000 g/mol.

Also employable according to the invention are mixtures of differentpolytetrahydrofurans, i.e. mixtures of polytetrahydrofurans havingdifferent molecular weights.

In a further embodiment the present invention therefore also relates toa thermoplastic polyurethane as described hereinabove, wherein thepolyol composition comprises a polyol (P1) selected from the groupconsisting of polytetrahydrofurans having a number-average molecularweight Mn in the range from 1501 g/mol to 3000 g/mol and a polyol (P2)selected from the group consisting of polytetrahydrofurans having anumber-average molecular weight Mn in the range from 500 g/mol to 1500g/mol.

It is customary to employ mixtures which comprise a polytetrahydrofuranhaving a number-average molecular weight Mn in the range from 1501 g/molto 3000 g/mol in an amount in the range from 5% to 30% and thepolytetrahydrofuran having a number-average molecular weight Mn in therange from 500 g/mol to 1500 g/mol in an amount in the range from 2% to50%.

According to the invention production of the thermoplastic polyurethaneemploys a polyisocyanate composition.

Preferred polyisocyanates in the context of the present invention arediisocyanates, in particular aliphatic or aromatic diisocyanates, morepreferably aromatic diisocyanates.

Also employable as isocyanate components in the context of the presentinvention are pre-reacted products in which some of the OH componentshave been reacted with an isocyanate in a preceding reaction step. Theobtained products are reacted with the remaining OH components in asubsequent step, the actual polymer reaction, thus forming thethermoplastic polyurethane.

Aliphatic diisocyanates employed are customary aliphatic and/orcycloaliphatic diisocyanates, for example tri-, tetra-, penta-, hexa-,hepta- and/or octamethylene diisocyanate, 2-methylpentamethylene1,5-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, hexamethylene1,6-diisocyanate (HDI), pentamethylene 1,5-diisocyanate, butylene1,4-diisocyanate, trimethylhexamethylene 1,6-diisocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophoronediisocyanate, IPDI), 1,4- and/or 1,3-bis(isocyanatomethyl)cyclohexane(HXDI), cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4- and/or2,6-diisocyanate, methylenedicyclohexyl 4,4′-, 2,4′- and/or2,2′-diisocyanate (H12MDI).

Preferred aliphatic polyisocyanates are hexamethylene 1,6-diisocyanate(HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and4,4′-, 2,4′- and/or 2,2′-methylene dicyclohexyldiisocyanate (H12MDI).

Preferred aliphatic polyisocyanates are hexamethylene 1,6-diisocyanate(HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and4,4′-, 2,4′- and/or 2,2′-methylenedicyclohexyl diisocyanate (H12MDI);especially preferred are 4,4′-, 2,4′- and/or 2,2′-methylenedicyclohexyldiisocyanate (H12MDI) and1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane or mixturesthereof.

Suitable aromatic diisocyanates are in particular 1,5-naphthylenediisocyanate (NDI), 2,4- and/or 2,6-tolylene diisocyanate (TDI), 2,2′-,2,4′- and/or 4,4′-diphenylmethane diisocyanate (MDI)3,3′-dimethyl-4,4′-diisocyanatobiphenyl (TODI), p-phenylene diisocyanate(PDI), 4,4′-diphenylethane diisocyanate (EDI), diphenylmethanediisocyanate, 3,3′-dimethyldiphenyl diisocyanate, 1,2-diphenylethanediisocyanate and/or phenylene diisocyanate.

In a preferred embodiment of the present invention only one isocyanateis employed. In particular it is preferably the case that mixturescomprising 4,4′-MDI and a further isocyanate are not employed.

Preferred examples of polyfunctional isocyanates are triisocyanates, forexample triphenylmethane 4,4′,4″-triisocyanate, and also the cyanuratesof the aforementioned diisocyanates and the oligomers obtainable bypartial reaction of diisocyanates with water, for example the biurets ofthe aforementioned diisocyanates, and oligomers obtainable by specificreaction of semi-blocked diisocyanates with polyols having on averagemore than two and preferably three or more hydroxyl groups.

According to the invention the polyisocyanate composition may alsocomprise one or more solvents. Suitable solvents are known to thoseskilled in the art. Suitable examples are nonreactive solvents such asethyl acetate, methyl ethyl ketone and hydrocarbons.

Also employable in the context of the present invention arecrosslinkers, for example the aforementioned polyfunctionalpolyisocyanates or polyols or else other polyfunctional molecules havinga plurality of isocyanate-reactive functional groups. It is likewisepossible in the context of the present invention to achieve crosslinkingof the products through an excess of the employed isocyanate groups overthe hydroxyl groups.

According to the invention the components (i) to (iii) are employed in aratio such that the molar ratio of the sum of the functionalities of theemployed polyol composition and chain extender to the sum of thefunctionalities of the employed isocyanate composition is in the rangefrom 1:0.8 to 1:1.3. The ratio is preferably in the range from 1:0.9 to1:1.2, more preferably in the range from 1:0.965 to 1:1.11, morepreferably in the range from 1:0.97 to 1:1.11, more preferably in therange from 1:0.97 to 1:1.05, particularly preferably in the range from1:0.98 to 1:1.03.

In a further embodiment the present invention relates to a thermoplasticpolyurethane as described hereinabove, wherein the molar ratio of thesum of the functionalities of the employed polyol composition and chainextender to the sum of the functionalities of the employed isocyanatecomposition is in the range from 1:0.8 to 1:1.3.

A further parameter considered in the reaction of the components (i) to(iii) is the isocyanate index. The index is defined by the ratio of allof the isocyanate groups of component (i) employed in the reaction tothe isocyanate-reactive groups, i.e. in particular the groups of thecomponents (ii) and (iii). At an index of 1000 there is one activehydrogen atom for each isocyanate group of component (i). At indicesabove 1000 there are more isocyanate groups than isocyanate-reactivegroups. The index in the reaction of the components (i) to (iii) ispreferably in the range from 965 to 1110, for example in the range from970 to 1110, more preferably in the range from 970 to 1050, particularlypreferably in the range from 980 to 1030.

In a further embodiment the present invention relates to a thermoplasticpolyurethane as described hereinabove, wherein the index in the reactionis in the range from 965 to 1100.

According to the invention further additives, for example catalysts orauxiliaries and additive, may be added during the reaction of thecomponents (i) to (iii). Additives and auxiliaries are known per se tothose skilled in the art. Combinations of two or more additives may alsobe employed according to the invention.

In the context of the present invention the term additive is to beunderstood as meaning in particular catalysts, auxiliaries andadditives, in particular stabilizers, nucleating agents, release agents,demolding agents, fillers, flame retardants or crosslinkers.

Suitable additives are for example stabilizers, nucleating agents,fillers, for example silicates, or crosslinkers, for examplepolyfunctional aluminosilicates.

In a further embodiment the present invention accordingly relates to athermoplastic polyurethane as described hereinabove, wherein thethermoplastic polyurethane comprises at least one additive.

Examples of auxiliaries and additives include surface-active substances,flame retardants, nucleating agents, oxidation stabilizers,antioxidants, lubricants and demolding aids, dyes and pigments,stabilizers, for example against hydrolysis, light, heat ordiscoloration, inorganic and/or organic fillers, reinforcers andplasticizers. Suitable auxiliaries and additives can be found, forexample, in Kunststoffhandbuch, volume VII, edited by Vieweg andHöchtlen, Carl Hanser Verlag, Munich 1966 (p. 103-113).

Suitable catalysts are likewise known in principle from the prior art.Suitable catalysts are for example organic metal compounds selected fromthe group consisting of tin, titanium, zirconium, hafnium, bismuth,zinc, aluminum and iron organyls, for example tin organyl compounds,preferably tin dialkyl compounds such as dimethyltin or diethyltin, ortin organyl compounds of aliphatic carboxylic acids, preferably tindiacetate, tin dilaurate, dibutyltin diacetate, dibutyltin dilaurate,bismuth compounds, such as bismuth alkyl compounds or the like, or ironcompounds, preferably iron(MI) acetylacetonate, or the metal salts ofcarboxylic acids, for example tin(II) isooctoate, tin dioctoate,titanate esters or bismuth(III) neodecanoate.

In a preferred embodiment the catalysts are selected from tin compoundsand bismuth compounds, more preferably tin alkyl compounds or bismuthalkyl compounds. Tin(II) isooctoate and bismuth neodecanoate areparticularly suitable.

The catalysts are typically employed in amounts of 0 to 2000 ppm,preferably 1 ppm to 1000 ppm, more preferably 2 ppm to 500 ppm and mostpreferably of 5 ppm to 300 ppm.

Properties of the thermoplastic polyurethanes according to the inventionmay be varied within wide ranges depending on the application.

The hard segment fraction in the thermoplastic polyurethanes accordingto the invention is typically in the range from 5% to 70%, in particularin the range from 10% to 50%, preferably in the range from 15% to 45%.In the context of the present invention the hard segment fraction isdetermined according to the formula disclosed in WO 2007/118827 A1.

In a further aspect the present invention also relates to a process forproducing a thermoplastic polyurethane comprising the reaction of atleast the components (i) to (iii):

-   -   (i) at least one polyisocyanate composition;    -   (ii) at least one chain extender (KV1) of general formula (I),

-   -   -   wherein A is selected from O, N(R3), S, CH₂,            -   Q is selected from O, N(R3), S, CH₂,            -   R1 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                OH,            -   R2 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                CH₂—CH(CH₃)—OH, OH,            -   n is 0, 1, 2, 3, 4, 5, 6,            -   R3 is selected from CH₃, CH₂—CH₃,            -   and A and Q are not simultaneously CH₂,

    -   (iii) at least one polyol composition,        wherein at least one further chain extender (KV2) selected from        the group consisting of compounds having at least two        isocyanate-reactive groups having a molecular weight of <500        g/mol is employed.

In respect of preferred embodiments of the process, suitable inputmaterials or mixing ratios, reference is made to the foregoing whichapplies correspondingly.

The reaction of the components (i) to (iii) may in principle beperformed under reaction conditions known per se. The reaction may beperformed discontinuously or else continuously, for example in a beltprocess or a reaction extrusion process. Suitable processes aredescribed for example in EP 0 922 552 A1 or WO 2006/082183 A1.

In a preferred embodiment the reaction of the components (i) to (iii) iscarried out at temperatures higher than room temperature.

According to the invention the heating may be effected in any suitablemanner known to the person skilled in the art. The input materials maypreferably also be heated before addition, for example using heatablemetering units.

For example in a reaction using the reaction extrusion process thereaction is managed such that the zone temperature is in the range from170° C. to 245° C., preferably in the range from 180° C. to 235° C.,more preferably in the range from 190° C. to 230° C.

In a further embodiment the present invention thus further relates to aprocess for producing a thermoplastic polyurethane as describedhereinabove, wherein the reaction is effected using a reaction extrusionprocess and the zone temperature is in the range from 170° C. to 245° C.

According to the invention the process may also comprise further steps,for example a pre-treatment of the components or a post-treatment of theobtained thermoplastic polyurethane. In a further embodiment the presentinvention thus also relates to a process for producing a thermoplasticpolyurethane as described hereinabove, wherein the obtainedthermoplastic polyurethane is heat-treated after the reaction.

The thermoplastic polyurethane according to the invention/a polyurethaneobtained or obtainable by a process according to the invention may beused in a wide variety of ways. The thermoplastic polyurethanesaccording to the invention are in particular suitable for producingmoldings and films. Possible applications are for example seals, sealingrings, gaskets, sealing washers, sealing agents, sealing compositions,sealants or shoe outersoles. Further applications are for example hosesfor inter alia pneumatic applications, conveyor belts, films, packagingmaterial, cables, flooring applications, shock absorbers and soundabsorbers.

In a further aspect the present invention also relates to the use of athermoplastic polyurethane as described hereinabove or of athermoplastic polyurethane obtainable or obtained by a process accordingto the invention for producing extrusion products, films and moldedarticles, in particular for producing cable sheathings, hoses and seals.

In a further embodiment the present invention also relates to the use ofa thermoplastic polyurethane as described hereinabove or of athermoplastic polyurethane obtainable or obtained by a process accordingto the invention for producing extrusion products, films and moldedarticles, wherein the extrusion product, the film or the foil isreinforced with fillers.

It has been found that, surprisingly, the thermoplastic polyurethanesaccording to the invention or the thermoplastic polyurethanes obtainedby a process according to the invention are well-suited to producingfoamed materials. The thermoplastic polyurethanes according to theinvention may be processed into foamed materials in a manner known perse. Additives such as blowing agents, cell regulators, surface-activesubstances, nucleating agents, fillers, hollow microspheres and/orrelease agents are optionally employed. Suitable processes and additivesare disclosed for example in WO2014/198779 A1, in WO 2007/082838 A1 orWO 94/20568 A1.

In a further aspect the present invention accordingly also relates tothe use of a thermoplastic polyurethane as described hereinabove or of athermoplastic polyurethane obtainable or obtained by a process accordingto the invention for producing foamed films, foamed moldings or foamedparticles and to the particle foams obtained therefrom.

In a further embodiment the present invention also relates to the use ofa thermoplastic polyurethane as described hereinabove or of athermoplastic polyurethane obtainable or obtained by a process accordingto the invention for producing foamed films, foamed moldings or foamedparticles and to the particle foams obtainable therefrom, wherein thefoamed films, foamed moldings or foamed particles and particle foamsobtainable therefrom are reinforced with fillers.

In a preferred embodiment the chain extender mixture is chosen such thatthe TPU has a softening point below 190° C., preferably below 160° C.and very preferably below 150° C.

The softening temperature was determined by DMA (measured on a 2 mminjection molded sheet heat treated at 100° C. for 20 h in accordancewith DIN EN ISO 6721-1:2011 at a frequency of 1 Hz and a heating rate of20 K/min measured from −80° C. to 200° C.).

Further embodiments of the present invention are apparent from theclaims and the examples. It will be appreciated that the features of thesubject matter/processes/uses according to the invention that arerecited hereinabove and elucidated hereinbelow are usable not only inthe combination specified in each case but also in other combinationswithout departing from the scope of the invention. Thus for example thecombination of a preferred feature with a particularly preferred featureor of a feature not characterized further with a particularly preferredfeature etc. is also encompassed implicitly even if this combination isnot mentioned explicitly.

Exemplary embodiments of the present invention are described hereinbelowbut are not intended to restrict the present invention. In particular,the present invention also comprises embodiments that result from thedependency references and hence combinations specified hereinbelow.

-   1. A thermoplastic polyurethane obtainable or obtained by reaction    of at least the components (i) to (iii):    -   (i) at least one polyisocyanate composition;    -   (ii) at least one chain extender (KV1) of general formula (I),

-   -   -   wherein A is selected from O, N(R3), S, CH₂,            -   Q is selected from O, N(R3), S, CH₂,            -   R1 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                OH,            -   R2 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                CH₂—CH(CH₃)—OH, OH,            -   n is 0, 1, 2, 3, 4, 5 or 6,            -   R3 is selected from CH₃, CH₂—CH₃,            -   and A and Q are not simultaneously CH₂,

    -   (iii) at least one polyol composition,

    -   wherein at least one further chain extender (KV2) selected from        the group consisting of compounds having at least two        isocyanate-reactive groups having a molecular weight of <500        g/mol is employed.

-   2. The thermoplastic polyurethane according to embodiment 1, wherein    the chain extender (KV2) is selected from the group consisting of    aliphatic and aromatic diols having a molecular weight of <500    g/mol.

-   3. The thermoplastic polyurethane according to embodiment 1 or 2,    wherein the chain extender (KV1) of general formula (I) is    hydroquinone bis(2-hydroxyethyl)ether.

-   4. The thermoplastic polyurethane according to any of embodiments 1    to 3, wherein the at least one further chain extender (KV2) is    selected from aliphatic and aromatic diols having a molecular weight    of <350 g/mol.

-   5. The thermoplastic polyurethane according to any of embodiments 1    to 3, wherein the at least one further chain extender (KV2) is a    compound of general formula (II):

-   -   wherein A is selected from O, N(R3), S, CH₂,        -   Q is selected from O, N(R3), S, CH₂,        -   R1 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH, OH,        -   R2 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,            CH₂—CH(CH₃)—OH, OH,        -   n is 0, 1, 2, 3, 4, 5 or 6,        -   R3 is selected from CH₃, CH₂—CH₃.

-   6. The thermoplastic polyurethane according to any of embodiments 1    to 5, wherein the polyol composition comprises a polyol selected    from the group consisting of polyetherols, polyesterols,    polycaprolactone polyols and polycarbonate polyols.

-   7. The thermoplastic polyurethane according to any of embodiments 1    to 6, wherein the polyol composition comprises a polyol selected    from the group consisting of polytetrahydrofurans having a    number-average molecular weight Mn in the range from 500 g/mol to    5000 g/mol.

-   8. The thermoplastic polyurethane according to any of embodiments 1    to 7, wherein the polyol composition comprises a polyol (P1)    selected from the group consisting of polytetrahydrofurans having a    number-average molecular weight Mn in the range from 1501 g/mol to    3000 g/mol and a polyol (P2) selected from the group consisting of    polytetrahydrofurans having a number-average molecular weight Mn in    the range from 500 g/mol to 1500 g/mol.

-   9. The thermoplastic polyurethane according to any of embodiments 1    to 8, wherein the polyisocyanate composition comprises an isocyanate    selected from the group consisting of TODI, NDI, PDI, 4,4′-MDI and    2,4′-MDI.

-   10. The thermoplastic polyurethane according to any of embodiments 1    to 9, wherein the polyisocyanate composition comprises a mixture of    4,4′-MDI and 2,4′-MDI.

-   11. A thermoplastic polyurethane obtainable or obtained by reaction    of at least the components (i) to (iii):    -   (i) at least one polyisocyanate composition;    -   (ii) at least hydroquinone bis(2-hydroxyethyl)ether as chain        extender (KV1),    -   (iii) at least one polyol composition,    -   wherein at least one further chain extender (KV2) selected from        the group consisting of compounds having at least two        isocyanate-reactive groups having a molecular weight of <500        g/mol is employed.

-   12. A thermoplastic polyurethane obtainable or obtained by reaction    of at least the components (i) to (iii):    -   (i) at least one polyisocyanate composition;    -   (ii) at least hydroquinone bis(2-hydroxyethyl)ether as chain        extender (KV1),    -   (iii) at least one polyol composition,    -   wherein at least one further chain extender (KV2) is employed,        which is a compound of general formula (II):

-   -   -   wherein A is selected from O, N(R3), S, CH₂,            -   Q is selected from O, N(R3), S, CH₂,            -   R1 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                OH,            -   R2 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                CH₂—CH(CH₃)—OH, OH,            -   n is 0, 1, 2, 3, 4, 5 or 6,            -   R3 is selected from CH₃, CH₂—CH₃.

-   13. A thermoplastic polyurethane obtainable or obtained by reaction    of at least the components (i) to (iii):    -   (i) at least one polyisocyanate composition;    -   (ii) at least hydroquinone bis(2-hydroxyethyl)ether as chain        extender (KV1),    -   (iii) at least one polyol composition,    -   wherein at least one further chain extender (KV2) selected from        the group consisting of compounds having at least two        isocyanate-reactive groups having a molecular weight of <500        g/mol is employed and    -   wherein the polyol composition comprises a polyol (P1) selected        from the group consisting of polytetrahydrofurans having a        number-average molecular weight Mn in the range from 1501 g/mol        to 3000 g/mol and a polyol (P2) selected from the group        consisting of polytetrahydrofurans having a number-average        molecular weight Mn in the range from 500 g/mol to 1500 g/mol.

-   14. A thermoplastic polyurethane obtainable or obtained by reaction    of at least the components (i) to (iii):    -   (i) at least one polyisocyanate composition;    -   (ii) at least hydroquinone bis(2-hydroxyethyl)ether as chain        extender (KV1),    -   (iii) at least one polyol composition,    -   wherein at least one further chain extender (KV2) is employed,        which is a compound of general formula (II):

-   -   -   wherein A is selected from O, N(R3), S, CH₂,            -   Q is selected from O, N(R3), S, CH₂,            -   R1 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                OH,            -   R2 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                CH₂—CH(CH₃)—OH, OH,            -   n is 0, 1, 2, 3, 4, 5 or 6,            -   R3 is selected from CH₃, CH₂—CH₃, and

    -   wherein the polyol composition comprises a polyol (P1) selected        from the group consisting of polytetrahydrofurans having a        number-average molecular weight Mn in the range from 1501 g/mol        to 3000 g/mol and a polyol (P2) selected from the group        consisting of polytetrahydrofurans having a number-average        molecular weight Mn in the range from 500 g/mol to 1500 g/mol.

-   15. A process for producing a thermoplastic polyurethane comprising    the reaction of at least the components (i) to (iii):    -   (i) at least one polyisocyanate composition;    -   (ii) at least one chain extender (KV1) of general formula (I),

-   -   -   wherein A is selected from O, N(R3), S, CH₂,            -   Q is selected from O, N(R3), S, CH₂,            -   R1 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                OH,            -   R2 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                CH₂—CH(CH₃)—OH, OH,            -   n is 1, 2, 3, 4, 5, 6,            -   R3 is selected from CH₃, CH₂—CH₃,            -   and A and Q are not simultaneously CH₂,

    -   (iii) at least one polyol composition,

    -   wherein at least one further chain extender (KV2) selected from        the group consisting of compounds having at least two        isocyanate-reactive groups having a molecular weight of <500        g/mol is employed.

-   16. The process according to embodiment 15, wherein the chain    extender (KV2) is selected from the group consisting of aliphatic    and aromatic diols having a molecular weight of <500 g/mol.

-   17. The process according to embodiment 15 or 16, wherein the chain    extender (KV1) of general formula (I) is hydroquinone    bis(2-hydroxyethyl)ether.

-   18. The process according to any of embodiments 15 to 17, wherein    the at least one further chain extender (KV2) is selected from    aliphatic and aromatic diols having a molecular weight of <350    g/mol.

-   19. The process according to any of embodiments 15 to 18, wherein    the at least one further chain extender (KV2) is a compound of    general formula (II):

-   -   wherein A is selected from O, N(R3), S, CH₂,        -   Q is selected from O, N(R3), S, CH₂,        -   R1 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH, OH,        -   R2 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,            CH₂—CH(CH₃)—OH, OH,        -   n is 0, 1, 2, 3, 4, 5 or 6,        -   R3 is selected from CH₃, CH₂—CH₃.

-   20. The process according to any of embodiments 15 to 19, wherein    the polyol composition comprises a polyol selected from the group    consisting of polyetherols, polyesterols, polycaprolactone polyols    and polycarbonate polyols.

-   21. The process according to any of embodiments 15 to 20, wherein    the polyol composition comprises a polyol selected from the group    consisting of polytetrahydrofurans having a number-average molecular    weight Mn in the range from 500 g/mol to 5000 g/mol.

-   22. The process according to any of embodiments 15 to 21, wherein    the polyol composition comprises a polyol (P1) selected from the    group consisting of polytetrahydrofurans having a number-average    molecular weight Mn in the range from 1501 g/mol to 3000 g/mol and a    polyol (P2) selected from the group consisting of    polytetrahydrofurans having a number-average molecular weight Mn in    the range from 500 g/mol to 1500 g/mol.

-   23. The process according to any of embodiments 15 to 22, wherein    the polyisocyanate composition comprises an isocyanate selected from    the group consisting of TODI, NDI, PDI, 4,4′-MDI and 2,4′-MDI.

-   24. The process according to any of embodiments 15 to 23, wherein    the polyisocyanate composition comprises a mixture of 4,4′-MDI and    2,4′-MDI.

-   25. A process for producing a thermoplastic polyurethane comprising    the reaction of at least the components (i) to (iii):    -   (i) at least one polyisocyanate composition;    -   (ii) at least hydroquinone bis(2-hydroxyethyl)ether as chain        extender (KV1),    -   (iii) at least one polyol composition,    -   wherein at least one further chain extender (KV2) selected from        the group consisting of compounds having at least two        isocyanate-reactive groups having a molecular weight of <500        g/mol is employed.

-   26. A process for producing a thermoplastic polyurethane comprising    the reaction of at least the components (i) to (iii):    -   (i) at least one polyisocyanate composition;    -   (ii) at least hydroquinone bis(2-hydroxyethyl)ether as chain        extender (KV1),    -   (iii) at least one polyol composition,    -   wherein at least one further chain extender (KV2) is employed,        which is a compound of general formula (II):

-   -   -   wherein A is selected from O, N(R3), S, CH₂,            -   Q is selected from O, N(R3), S, CH₂,            -   R1 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                OH,            -   R2 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                CH₂—CH(CH₃)—OH, OH,            -   n is 0, 1, 2, 3, 4, 5 or 6,            -   R3 is selected from CH₃, CH₂—CH₃.

-   27. A process for producing a thermoplastic polyurethane comprising    the reaction of at least the components (i) to (iii):    -   (i) at least one polyisocyanate composition;    -   (ii) at least hydroquinone bis(2-hydroxyethyl)ether as chain        extender (KV1),    -   (iii) at least one polyol composition,    -   wherein at least one further chain extender (KV2) selected from        the group consisting of compounds having at least two        isocyanate-reactive groups having a molecular weight of <500        g/mol is employed and    -   wherein the polyol composition comprises a polyol (P1) selected        from the group consisting of polytetrahydrofurans having a        number-average molecular weight Mn in the range from 1501 g/mol        to 3000 g/mol and a polyol (P2) selected from the group        consisting of polytetrahydrofurans having a number-average        molecular weight Mn in the range from 500 g/mol to 1500 g/mol.

-   28. A process for producing a thermoplastic polyurethane comprising    the reaction of at least the components (i) to (iii):    -   (i) at least one polyisocyanate composition;    -   (ii) at least hydroquinone bis(2-hydroxyethyl)ether as chain        extender (KV1),    -   (iii) at least one polyol composition,    -   wherein at least one further chain extender (KV2) is employed,        which is a compound of general formula (II):

-   -   -   wherein A is selected from O, N(R3), S, CH₂,            -   Q is selected from O, N(R3), S, CH₂,            -   R1 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                OH,            -   R2 is selected from CH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH,                CH₂—CH(CH₃)—OH, OH,            -   n is 0, 1, 2, 3, 4, 5 or 6,            -   R3 is selected from CH₃, CH₂—CH₃, and

    -   wherein the polyol composition comprises a polyol (P1) selected        from the group consisting of polytetrahydrofurans having a        number-average molecular weight Mn in the range from 1501 g/mol        to 3000 g/mol and a polyol (P2) selected from the group        consisting of polytetrahydrofurans having a number-average        molecular weight Mn in the range from 500 g/mol to 1500 g/mol.

-   29. The use of a thermoplastic polyurethane according to any of    embodiments 1 to 14 or of a thermoplastic polyurethane obtainable or    obtained by a process according to any of embodiments 15 to 28 for    producing extrusion products, films and molded articles, in    particular for producing cable sheathings, hoses and seals.

-   30. The use according to embodiment 29, wherein the extrusion    product, the film or the foil is reinforced with fillers.

-   31. The use of a thermoplastic polyurethane according to any of    embodiments 1 to 14 or of a thermoplastic polyurethane obtainable or    obtained by a process according to any of embodiments 15 to 28 for    producing foamed films, foamed moldings or foamed particles and    particle foams obtainable therefrom.

-   32. The use according to embodiment 31, wherein the foamed films,    foamed moldings or foamed particles and particle foams obtainable    therefrom are reinforced with fillers.

BRIEF DESCRIPTION OF THE FIGURES

FIGS. 1A-1D show hoses produced from a thermoplastic polyurethane,wherein the thermoplastic polyurethane consists of PTHF1000 and thespecified hard phase and has a shore hardness of 98A. The materials wereproduced on a pilot reaction extruder.

FIG. 1A and FIG. 1B show a hose made of a thermoplastic polyurethanecomprising an HQEE-MDI hard phase.

FIG. 1C and FIG. 1D show a hose made of a thermoplastic polyurethanecomprising TPU comprising an HQEE/HER-MDI hard phase.

The examples which follow are intended to illustrate the invention butare in no way intended to restrict the subject matter of the presentinvention.

EXAMPLES

1 The Following Input Materials were Used:

-   -   PTHF 1000: Polytetramethylene oxide (PTHF) Mw 1000 g/mol    -   PTHF 650: Polytetramethylene oxide (PTHF) Mw 650 g/mol    -   PTHF 2000: Polytetramethylene oxide (PTHF) Mw 2000 g/mol    -   HQEE: Hydroquinone bis(2-hydroxyethyl)ether    -   4,4′-MDI: 4,4′-diphenylmethane diisocyanate    -   TODI: 3,3′-dimethyl-4,4′-di isocyanatobiphenyl    -   HER: Resorcinol bis(2-hydroxyethyl)ether 1,4-Butanediol    -   Irganox 1010 FF (CAS No. 6683-19-8) and 1098 (CAS No.        23128-74-7)        2 Synthesis of the Polyurethanes

2.1 Polyurethane Based on HQEE, 4,4-MDI and PTHF (Comparative Example)

-   -   800.00 g of PolyTHF1000 together with 238.84 g of HQEE were        weighed into a 2 L tinplate can and briefly blanketed with        nitrogen. The can was sealed with a suitable lid and heated to        about 120° C. in a heating cabinet.    -   The liquid components in the can were mixed with a propeller        stirrer on a lift. Subsequently 7.81 g of Irganox 1010 FF and        7.81 g of Irganox 1098 were added and the mixture was stirred.    -   The temperature of the mixture was carefully adjusted to 108° C.        with a hot air gun. Addition of 505.1 g of 4,4′-MDI was carried        out at 108° C. ( ). The MDI had a temperature of 45° C.        Commixing was effected using a propeller stirrer at 200 rpm.        Upon reaching 110° C. the reaction mixture was poured into a        Teflon dish. The Teflon dish was situated on a hotplate at 125°        C.    -   The solid slab was removed from the hotplate after 10 min and        then heat treated in a heating cabinet at 80° C. for 24 h. The        cooled slab was comminuted in a cutting mill. The resulting        granulate was dried at 110° C. for 3 h. 2 mm and 6 mm test        specimens were produced by injection molding methods.

2.2 Polyurethane Based on an HQEE and 1,4-Butanediol Mixture (Example 1)

-   -   800.00 g of PolyTHF1000 together with 235.49 g of HQEE and 11.96        g of HER and 2.19 g of 1,4-butanediol were weighed into a 2 L        tinplate can and briefly blanketed with nitrogen. The can was        sealed with a suitable lid and heated to about 120° C. in a        heating cabinet.    -   The liquid components in the can were mixed with a propeller        stirrer on a lift. Subsequently 7.81 g of Irganox 1010 FF and        7.81 g of Irganox 1098 were added and the mixture was stirred.    -   The temperature of the mixture was carefully adjusted to 108° C.        with a hot air gun. Addition of 508.18 g of 4,4′-MDI was carried        out at 108° C. ( ). The MDI had a temperature of 45° C.        Commixing was effected using a propeller stirrer at 200 rpm.        Upon reaching 110° C. the reaction mixture was poured into a        Teflon dish. The Teflon dish was situated on a hotplate at 125°        C.    -   The solid slab was removed from the hotplate after 10 min and        then heat treated in a heating cabinet at 80° C. for 24 h. The        cooled slab was comminuted in a cutting mill. The resulting        granulate was dried at 110° C. for 3 h. 2 mm and 6 mm test        specimens were produced by injection molding methods.

2.3 Example 2

-   -   Production was carried out by the same production process as        described in connection with example 1 but 5% 1,4-butanediol was        used. The input materials are summarized in table 1.

2.4 Example 3

-   -   Production was carried out by the same production process as        described in connection with example 1 but 10% 1,4-butanediol        was used. The input materials are summarized in table 1.

2.5 Polyurethane Based on an HQEE and HER Mixture (Example 4)

800.00 g of PolyTHF1000 together with 227.18 g of HQEE and 11.96 g ofHER were weighed into a 2 L tinplate can and briefly blanketed withnitrogen. The can was sealed with a suitable lid and heated to about120° C. in a heating cabinet.

The liquid components in the can were mixed with a propeller stirrer ona lift. Subsequently 7.81 g of Irganox 1010 FF and 7.81 g of Irganox1098 were added and the mixture was stirred.

The temperature of the mixture was carefully adjusted to 108° C. with ahot air gun. Addition of 506.72 g of 4,4′-MDI was carried out at 108° C.The MDI had a temperature of 45° C. Commixing was effected using apropeller stirrer at 200 rpm. Upon reaching 110° C. the reaction mixturewas poured into a Teflon dish. The Teflon dish was situated on ahotplate at 125° C.

The solid slab was removed from the hotplate after 10 min and then heattreated in a heating cabinet at 80° C. for 24 h. The cooled slab wascomminuted in a cutting mill. The resulting granulate was dried at 110°C. for 3 h. 2 mm and 6 mm test specimens were produced by injectionmolding methods.

2.6 Example 5

Production was carried out by the same production process as describedin connection with example 4 but 10% HER was used. The input materialsare summarized in table 1.

2.7 Example 6

Production was carried out by the same production process as describedin connection with example 4 but 50% HER was used. The input materialsare summarized in table 1.

2.8 Polyurethane Based on an HQEE and PTHF Mixture (Example 7)

760.00 g of PolyTHF2000 and 40.00 g of PolyTHF650s together with 268.52g of HQEE were weighed into a 2 L tinplate can and briefly blanketedwith nitrogen. The can was sealed with a suitable lid and heated toabout 120° C. in a heating cabinet.

The liquid components in the can were mixed with a propeller stirrer ona lift. Subsequently 7.68 g of Irganox 1010 FF and 7.68 g of Irganox1098 were added and the mixture was stirred.

The temperature of the mixture was carefully adjusted to 108° C. with ahot air gun. Addition of 451.23 g of 4,4′-MDI was carried out at 108° C.The MDI had a temperature of 45° C. Commixing was effected using apropeller stirrer at 200 rpm. Upon reaching 110° C. the reaction mixturewas poured into a Teflon dish. The Teflon dish was situated on ahotplate at 125° C.

The solid slab was removed from the hotplate after 10 min and then heattreated in a heating cabinet at 80° C. for 24 h. The cooled slab wascomminuted in a cutting mill. The resulting granulate was dried at 110°C. for 3 h. 2 mm and 6 mm test specimens were produced by injectionmolding methods.

2.9 Example 8

Production was carried out by the same production process as describedin connection with example 7 but 10% PolyTHF650s was used. The inputmaterials are summarized in table 1.

2.10 Example 9

Production was carried out by the same production process as describedin connection with example 7 but 20% PolyTHF650s was used. The inputmaterials are summarized in table 1.

TABLE 1 Employed compounds Example 2 Example 3 Example 5 Example 6Example 8 Example 9 PolyTHF 1000 800.00 g 800.00 g 800.00 g 800.00 g1,4-Butanediol  5.50 g  11.14 g PolyTHF 2000 720.00 g 640.00 g PolyTHF650s  80.00 g 160.00 g HQEE 229.95 g 220.54 g 215.22 g 119.57 g 271.61 g277.81 g HER  23.91 g 119.57 g 4,4-MDI 510.40 g 514.18 g 506.72 g 506.72g 465.66 g 494.53 g Irganox 1010 FF  7.81 g  7.81 g  7.81 g  7.81 g 7.76 g  7.94 g Irganox 1098  7.81 g  7.81 g  7.81 g  7.81 g  7.76 g 7.94 g

2.11 Variation of the HQEE/HER Ratio (Examples 10 to 18)

The examples were produced analogously to example 1. The ratio of thechain extenders was varied according to table 2.

TABLE 2 Mixing ratios for examples 10 to 18 HS proportion Test ExampleReactants [%] sheets Index Example 10 PTHF1000, HQEE + 35.0% translucent1000 HER (9.5:0.5) and MDI Example 11 PTHF1000, HQEE + 35.0% translucent1000 HER (9:1) and MDI Example 12 PTHF1000, HQEE + 35.0% transparent1000 HER (5:5) and MDI Example 13 PTHF1000, HQEE + 35.0% transparent1000 HER (8.5:1.5) and MDI Example 14 PTHF1000, HQEE + 35.0% transparent1000 HER (8:2) and MDI Example 15 PTHF1000, HQEE + 35.0% transparent1000 HER (7.5:2.5) and MDI Example 16 PTHF1000, HQEE + 35.0% transparent1000 HER (7:3) and MDI Example 17 PTHF1000, HQEE + 35.0% transparent1000 HER (6.5:3.5) and MDI Example 18 PTHF1000, HQEE + 35.0% transparent1000 HER (5.5:4.5) and MDI3 Mechanical Properties

3.1 The measured values summarized in tables 3a and 3b were obtainedfrom injection molded sheets/from extrusion products of the obtainedpolyurethanes.

TABLE 3a Mechanical properties Elongation at break Tensile Elongationstrength at break Example Shore hardness RT 80° C. (RT) 80° C. number[Shore A] [Shore D] [MPa] [MPa] [%] [%] Example 1 95 53 54 26 490 630Example 2 95 53 51 20 520 620 Example 3 94 51 42 19 500 590 Comparative95 52 34 18 480 640 example 1

TABLE 3b Mechanical properties Compression set Tear 72 h/ 24 h/ 24 h/propagation 23° C./ 70° C./ 100° C./ Example resistance Abrasion Density30 min 30 min 30 min number [N/mm] [mm³] [g/cm³] [%] [%] [%] Example 1105 34 1.144 15 27 41 Example 2 100 43 1.144 16 31 46 Example 3  94 471.142 15 33 46 Com-  88 61 1.144 22 30 43 parative example 1

3.2 The measured values summarized in tables 4a and 4b were obtainedfrom injection molded sheets/extrusion products of the obtainedpolyurethanes according to examples 10 to 18.

TABLE 4a Mechanical properties Elongation at break Tensile Elongationstrength at break Example Shore hardness RT 80° C. (RT) 80° C. number[Shore A] [Shore D] [MPa] [MPa] [%] [%] Example 10 — 52 52 16 520 650Example 11 — 52 51 16 510 680 Example 12 — 46 48 14 480 750 Example 1394 50 36 17 460 640 Example 14 93 50 38 15 470 540 Example 15 93 48 3814 470 500 Example 16 91 48 42 16 460 580 Example 17 91 47 38 14 460 500Example 18 89 45 45 16 460 510

TABLE 4b Mechanical properties Compression set Tear prop- 72 h/ 24 h/ 24h/ agation 23° C./ 70° C./ 100° C./ Example resistance Abrasion Density30 min 30 min 30 min number [N/mm] [mm³] [g/cm³] [%] [%] [%] Example 1090 43 1.144 16 32 31 Example 11 90 46 1.143 16 15 35 Example 12 82 351.143 15 20 46 Example 13 92 50 1.143 11 34 47 Example 14 89 45 1.142 1126 50 Example 15 86 46 1.142 19 29 49 Example 16 93 39 1.141 21 32 43Example 17 95 38 1.143 20 33 46 Example 18 86 37 1.143 16 31 50

3.3 The following properties of the obtained polyurethanes weredetermined by the recited methods:

-   -   Hardness: DIN ISO 7619-1    -   Tensile strength and elongation at break: DIN 53504    -   Tear propagation resistance: DIN ISO 34-1, B (b)    -   Abrasion measurement: DIN ISO 4649    -   Density: DIN EN ISO 1183-1, A    -   Compression set DIN ISO 815        4 Extrusion Quality

The images reproduced in FIGS. 1A-1D show the different hose extrusionqualities of a TPU consisting of PTHF 1000, the recited hard phase and ashore hardness of 98A produced on a pilot reaction extruder. Materialsobtained by manual casting had a comparable appearance.

Hoses were produced from the materials of comparative example 1 andexample 5. Hose production was carried out using a 45 mm single-screwextruder from Arenz (3-zone screw, compression ratio 1:2.5). The hoseshad dimensions of 8.2 mm×5.8 mm.

FIG. 1A and FIG. 1B show a hose made of a thermoplastic polyurethanecomprising an HQEE-MDI hard phase (according to comparative example 1).

FIG. 1C and FIG. 1D show a hose made of a thermoplastic polyurethanecomprising TPU comprising an HQEE/HER-MDI hard phase (according toexample 5).

CITED LITERATURE

-   WO 2006/082183 A1-   EP 0 922 552 A1-   WO 98/56845-   “Kunststoffhandbuch”, volume 7, “Polyurethane”, Carl Hanser Verlag,    3rd edition, 1993, chapter 3.1-   “Kunststoffhandbuch”, volume VII, edited by Vieweg and Höchtlen,    Carl Hanser Verlag, Munich, 1966 (pp. 103-113)-   WO 2007/118827 A1-   EP 0 922 552 A1-   WO 2006/082183 A1-   WO2014/198779 A1-   WO 2007/082838 A1-   WO 94/20568 A1

The invention claimed is:
 1. A thermoplastic polyurethane obtained byreaction of at least a polyisocyanate composition; hydroxyquinonebis(2-hydroxyethyl)ether as a first chain extender; a polyolcomposition; and a second chain extender, wherein the second chainextender has at least two isocyanate-reactive groups and has a molecularweight of <500 g/mol, and the second chain extender is a compound ofgeneral formula (II):

wherein A is O, N(R3), S, or CH₂, Q is O, N(R3), S, or CH₂, R1 isCH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH, or OH, R2 is CH₂—(CH₂)_(n)—OH,CH(CH₃)—CH₂—OH, CH₂—CH(CH₃)—OH, or OH, n is 0, 1, 2, 3, 4, 5 or 6, andR3 is CH₃, or CH₂—CH₃, wherein a molar ratio of hydroquinonebis(2-hydroxyethyl)ether to the second chain extender is in a range of9:1 to 19:1; and the polyol present in the polyol composition is apolyetherol.
 2. The thermoplastic polyurethane according to claim 1,wherein said polyetherol is a polytetrahydrofuran having anumber-average molecular weight Mn in a range from 500 g/mol to 5000g/mol.
 3. The thermoplastic polyurethane according to claim 1, whereinsaid polyetherol comprises a polytetrahydrofuran having a number-averagemolecular weight Mn in a range from 1501 g/mol to 3000 g/mol and apolytetrahydrofuran having a number-average molecular weight Mn in arange from 500 g/mol to 1500 g/mol.
 4. The thermoplastic polyurethaneaccording to claim 1, wherein the polyisocyanate composition comprisesan isocyanate selected from the group consisting of3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 1,5-naphthylene diisoctanate,p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate and2,4′-diphenylmethane diisocyanate.
 5. The thermoplastic polyurethaneaccording to claim 1, wherein the polyisocyanate composition comprises amixture of 4,4′-diphenylmethane diisocyanate and 2,4′-diphenylmethanediisocyanate.
 6. A process for producing a thermoplastic polyurethane,the process comprising: reacting polyisocyanate composition;hydroxyquinone bis(2-hydroxyethyl)ether as a first chain extender; apolyol composition; and a second chain extender, wherein the secondchain extender has at least two isocyanate-reactive groups and has amolecular weight of <500 g/mol and the second chain extender is acompound of general formula (II):

wherein A is O, N(R3), S, or CH₂, Q is O, N(R3), S, or CH₂, R1 isCH₂—(CH₂)_(n)—OH, CH(CH₃)—CH₂—OH, or OH, R2 is CH₂—(CH₂)_(n)—OH,CH(CH₃)—CH₂—OH, CH₂—CH(CH₃)—OH, or OH, n is 0, 1, 2, 3, 4, 5 or 6, andR3 is CH₃, or CH₂—CH₃, wherein a molar ratio of hydroquinonebis(2-hydroxyethyl)ether to the second chain extender is in a range of9:1 to 19:1; and the polyol present in the polyol composition is apolyetherol.
 7. An article, comprising the thermoplastic polyurethaneaccording to claim 1, wherein the article is an extrusion product, afilm or a molded article.
 8. The article according to claim 7, whereinthe article is an extrusion product or a film, and the extrusion productor the film is reinforced with fillers.
 9. An article, comprising thethermoplastic polyurethane according to claim 1, wherein the article isa foamed film, a foamed molding, foamed particles or particle foamsobtained therefrom.
 10. The article according to claim 9, wherein thearticle is reinforced with fillers.
 11. The thermoplastic polyurethaneaccording to claim 1, where A and Q are each independently O, N(R3),orS.
 12. The thermoplastic polyurethane according to claim 1, wherein saidsecond chain extender is resorcinol bis(2-hydroxyethyl)ether.
 13. Thethermoplastic polyurethane according to claim 1, wherein saidthermoplastic polyurethane has a room temperature tensile strength of 51MPa to 52 MPa.
 14. The thermoplastic polyurethane according to claim 1,wherein said thermoplastic polyurethane has a room temperatureelongation at break of 510% to 520%.
 15. The thermoplastic polyurethaneaccording to claim 1, wherein an amount of said second chain extender is5 to 10% based on a total amount of chain extender.
 16. The processaccording to claim 6, wherein an amount of said second chain extender is5 to 10% based on a total amount of chain extender.